U.S. patent number 4,548,977 [Application Number 06/679,141] was granted by the patent office on 1985-10-22 for polymer slurry preparation.
This patent grant is currently assigned to Phillips Petroleum Company. Invention is credited to Aubrey South, Jr..
United States Patent |
4,548,977 |
South, Jr. |
October 22, 1985 |
Polymer slurry preparation
Abstract
A process for producing poly(arylene sulfide) resin slurries
exhibiting easier handling and improved performance properties
suitable for coating, molding, etc. comprising mixing the polymer
with a nonionic surfactant in the absence of a liquid diluent and
then blending the resulting admixture with a reinforcing material
in a liquid diluent.
Inventors: |
South, Jr.; Aubrey
(Bartlesville, OK) |
Assignee: |
Phillips Petroleum Company
(Bartlesville, OK)
|
Family
ID: |
24725732 |
Appl.
No.: |
06/679,141 |
Filed: |
December 6, 1984 |
Current U.S.
Class: |
524/310;
524/609 |
Current CPC
Class: |
C08J
3/21 (20130101); C08J 2381/02 (20130101) |
Current International
Class: |
C08J
3/20 (20060101); C08J 3/21 (20060101); C08K
005/10 () |
Field of
Search: |
;524/310,308,609 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Jacobs; Lewis T.
Attorney, Agent or Firm: Doescher; Howard P.
Claims
That which is claimed is:
1. A process for producing poly(arylene sulfide) slurries suitable
for coating and molding comprising:
(a) combining 100 weight parts solid poly(arylene sulfide) resin
with at least about 0.5 weight parts of at least one nonionic
surfactant under conditions to produce an intimate admixture,
and
(b) blending the admixture obtained in (a) with a reinforcing
material in a liquid diluent medium.
2. A process according to claim 1 wherein said reinforcing material
is glass fibers and said diluent is water.
3. A process according to claim 1 wherein said nonionic surfactant
is a polyoxyethylated vegetable oil.
4. A process according to claim 1 wherein said poly(arylene
sulfide) resin is poly(phenylene sulfide).
5. A process according to claim 1 wherein said poly(arylene
sulfide) resin is poly(phenylene sulfide), said diluent is water,
and said reinforcing material is glass fibers.
6. A process according to claim 1, wherein based on 100 parts
weight of said resin, the composition contains from about 0.5 to
about 10 weight parts nonionic surfactant, about 10-100 weight
parts glass fibers, and about 50-200 weight parts diluent.
7. A process according to claim 6, wherein said nonionic surfactant
is a polyoxyethylated vegetable oil.
8. A process according to claim 7 wherein said nonionic surfactant
is polyoxyethylated castor oil and said resin is poly(phenylene
sulfide).
Description
BACKGROUND OF THE INVENTION
This invention relates to improved poly(arylene sulfide)
compositions and to methods of preparing poly(arylene sulfide)
resin slurries.
Arylene sulfide polymers are ideally suited for a wide variety of
uses because of the high temperature stability of such polymers and
their ability to withstand chemical attack. These polymers are
known for their desirable characteristics as coating compositions
and for molding into a variety of products. It is often desirable
to incorporate various reinforcing agents into arylene sulfide
polymers prior to use as coatings, molding compositions, and other
uses. It is often difficult to handle and process slurries and
dispersions of these polymers, especially when these compositions
contain high loadings of reinforcing agents and at the same time it
is desirable to obtain cured products having desirable performance
characteristics. The present invention is directed to the
preparation of arylene sulfide polymer slurries, which are easier
to handle and at the same time provide compositions that can be
cured into products having improved performance properties.
Accordingly, an object of this invention is to provide arylene
sulfide polymer compositions that can be easily handled and
processed
It is a further object of this invention to provide a method for
producing slurries of arylene sulfide polymers which can be readily
processed into products having desirable characteristics.
Other objects, aspects as well as the several advantages of the
invention will be apparent to those skilled in the art upon reading
the specification and the appended claims.
SUMMARY OF THE INVENTION
In accordance with the invention, slurries of arylene sulfide
polymers having desirable characteristics are produced by
intimately combining an arylene sulfide polymer with at least one
non-ionic surfactant in the absence of a liquid diluent, and then
blending the admixture thus formed with a reinforcing material in a
liquid diluent to produce a slurry. The slurry can then be further
processed and utilized as a coating composition, molding
composition, or other use as desired.
In a specific embodiment of the invention, a poly(phenylene
sulfide) known as PPS, composition prepared by separately
pre-mixing PPS and a nonionic surfactant comprising polyoxyethlated
vegetable oil followed by blending with a glass-fibers and water
not only provides an easier handling more pourable premix but when
cured results in a product exhibiting better performance properties
than products prepared from a mixture in which all of the
ingredients were simultaneously mixed together.
DETAILED DESCRIPTION OF THE INVENTION
The invention is applicable for use with any normally solid, heat
curable, high molecular weight arylene sulfide polymer that can be
formed into fiber, film, or other articles. Arylene sulfide
polymers which can be employed in the process of this invention
include arylene sulfide polymers which have a melt flow of at least
about 20 and generally within the range of about 50 to about 400
and higher (determined by the method of ASTM D 1238-70, modified
into a temperature of 316.degree. C. using a 5-kg weight, the value
being expressed as g/10 min.). Thus, the arylene sulfide polymers
can be linear, branched or lightly cross-linked. Although the
method by which the polymers of this description are produced is
not critical, preferably the polymers employed in the process is
prepared by use of polyhaloaromatic compounds, alkali metal
sulfides, and organic amides. For example, the arylene sulfide
polymers for use in this invention can be produced by the method of
U.S. Pat. No. 3,354,129 which is hereby incorporated by reference.
The preferred type polymer employed for use in fiber and film
applications is prepared by use of a p-dihalobenzene, an alkali
metal sulfide, an organic amide, and an alkali metal carboxylate as
in U.S. Pat. No. 3,919,177. The disclosure of U.S. Pat. No.
3,919,177 is hereby incorporated by reference.
The invention is applicable for use with any nonionic surfactant.
Suitable nonionic surfactants include polyoxyethylated vegetable
oils.
Specifically polyoxyethylated castor oil, polyoxyethylated saffron
flower oil, polyoxyethylated peanut oil, polyoxyethylated corn oil,
polyoxyethylated cottonseed oil, polyoxyethylated soya bean oil,
and the like, and mixture thereof are considered to be suitable. In
general it is considered desirable for the polyoxyethylated
vegetable oil to have an average number of oxyethylene groups per
molecule in the range of 6 to 30, and preferably in the range of 8
to 20. Presently preferred are polyoxyethylated derivatives of
castor oil having a viscosity at 25.degree. C. in the range of 500
to 1000 cps, a specific gravity in the range of 1.04 to 1.07, and a
flash point in the range of 275.degree. to 295.degree. C.
Other suitable nonionic surface active agents include ethoxylated
alkylphenols, ethoxylated aliphatic alcohols, carboxylic esters,
carboxylic amides, and polyoxyalkylene oxide block copolymers.
Preferred materials are alkylphenoxypoly(ethyleneoxy)ethanol.
Exemplary of such materials is the material sold by Rohm and Haas
under the trademark Triton X-100 wherein the alkyl is t-octyl and
the moles of ethylene oxide per mole of phenolic compound is within
the range of 9-10.
Other nonionic surfactants that can be used include ethoxylated
linear alcohols, alkylaryl polyether alcohols and the like,
including mixtures thereof.
The invention is also applicable for use with any suitable
reinforcing agent depending upon desired use of the final product.
Glass fibers are presently preferred as the reinforcing agent but
other reinforcing agents, such as silica, mineral fillers such as
talc, calcium carbonate, zinc oxide, iron oxide, titanium dioxide,
etc. and mixture thereof, can also be used.
Any liquid can be used as the diluent provided the liquid is inert
to the other components of the slurry and to the substrate, and
provided it is readily volatized prior to or during the subsequent
heating or curing step. The diluents presently preferred are water
and ethylene glycol. Other diluents which can be used include
alcohols such as methyl alcohol, ethyl alcohol, and isopropyl
alcohol, and hydrocarbons such as benzene, toluene, heptane,
cyclohexane, and various hydrocarbon mixtures such as kerosene,
diesel fuel, and the like. Less preferred diluents which can be
used include chlorinated biphenyl, dimethyl phthalate, and the
like. Mixtures of the diluents can be used.
The ranges for the ingredients used can be based on:
______________________________________ Ingredients parts by weight
______________________________________ PPS 100 Surfactant 0.5 to 10
(preferred 1 to 5) Glass Fibers 10-100 Water (diluent) 50-200
______________________________________
As indicated hereinbefore it is important that the nonionic surface
active agent be mixed with the arylene sulfide polymer, which is
preferably in particulate form, in the absence of a diluent or
liquid. Mixing of the polymer and surfactant can be carried out at
ambient conditions in any suitable mixing equipment.
Following preparation of the nonionic surfactant/arylene sulfide
polymer admixture, this admixture is then blended with a diluent
such as water containing a reinforcing material. This step of the
blending process can be carried out at ambient conditions also. Any
suitable type of mixing equipment can be used so long as an
intimate final mixture of polymer, surfactant, and reinforcing
material is obtained as a slurry having the desired characteristics
set forth herein.
The final dispersion of the invention can be utilized, for example,
as a coating composition by applying to a substrate by any
conventional means, such as spraying or with a blade or the like,
and then cured for instance by heating to an elevated temperature
of at least about 500.degree. F. It is also within the scope of the
invention to use the final dispersion as a molding composition by
charging to a suitable type of mold, and applying heat and pressure
to form a desired molded article.
EXAMPLE
This example describes the process used to illustrate the
operability of this invention by demonstrating the criticality in
the way surfactants are added to a glass-filled poly(phenylene
sulfide) composition during the initial ingredient compounding or
mixing process. To a one-gallon paint can was added 800 grams of
distilled water, 600 grams of poly(phenylene sulfide) (Ryton FS-2,
melt flow 100-140 grams/10 minutes as determined by test method
ASTM D 1238 at 600.degree. F., 316.degree. C., using a 5 kilogram
load), 16 grams of EL-620 surfactant (a polyoxyethylated castor oil
from GAF), and 400 grams of 1 inch chopped glass fibers (433-AC-227
from Owens Corning) and the mixture mechanically shaken on a RED
DEVIL paint mixer for 10 minutes. Molded plaques were then prepared
by placing 800 grams of the wet resin mixture into a 11 inch
.times. 11 inch .times. 0.15 inch mold and heated for 10 minutes at
600.degree. F. (316.degree. C.) in a press which was left partially
open to remove water. A slight pressure was then applied to the
mold by closing the press for 9 minutes while maintaining the same
temperature. A platen pressure of 15,000 pounds was applied at the
elevated temperature for 1 minute and then while maintaining the
15,000 pounds pressure the press was water cooled for 10 minutes.
The sample was cut into a 10 inch .times. 9 inch piece and placed
into a positive pressure press at 25 tons ram force for 10 minutes.
The sample was removed and cut into strips 8 inches .times. 1 inch
.times. 0.125 inch for tensile testing and 3 inches .times. 0.5
inch .times.0.125 inch for impact testing. Before the strips were
tested they were annealed for 2 hours at 350.degree. F.
(177.degree. C.).
The aforementioned process was repeated except the poly(phenylene
sulfide) polymer and polyoxyethylated castor oil surfactant were
premixed in a Waring blender for 1 to 3 minutes prior to the
subsequent mixing with water and glass fibers in the RED DEVIL
paint mixer. The premixing of the surfactant and poly(phenylene
sulfide) is the invention. The performance testing results from the
two described mixing procedures are listed in TABLE I where it can
be seen that the inventive premixing of polymer and surfactant
gives significantly improved molded performance properties. In
addition, a slurry from the process was easier to handle and poured
more freely than without pretreatment of the poly(phenylene
sulfide) polymer with the surfactant.
TABLE I ______________________________________ Effect of Surfactant
Addition on a Poly(Phenylene Sulfide)-Glass Fiber Composition Runs
(Pre-Mix) Control Invention ______________________________________
A. Composition: grams 1. Poly(phenylene sulfide)* 600 600 2.
Surfactant, EL-620** 16 16 3. Chopped glass, 1 inch 400 400 4.
Distilled water 800 800 B. Performance Properties (Molded) Test
Method 1. Tensile Modulus, MPa ASTM D 638 4077 4778 2. Tensile
Break, MPa ASTM D 638 18.2 43.4 3. Izod Impact, J/M ASTM D 256 a.
Notched 424 635 b. Unnotched 490 750
______________________________________ *Ryton FS2 from Phillips
Petroleum Company **Polyoxyethylated castor oil from GAF
* * * * *